Journal
INORGANIC CHEMISTRY FRONTIERS
Volume 3, Issue 10, Pages 1306-1316Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6qi00260a
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Funding
- National Science Centre [2013/11/D/ST8/03297]
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Two hybrid crystals imidazolium iodoantimonate(III) and iodobismuthate(III), (C3H5N2)(3)[Sb2I9] (ImIA) and (C3H5N2)(3)[Bi2I9] (ImIB), have been synthesized and characterized in a wide temperature range (100-350 K) by means of X-ray diffraction, dielectric spectroscopy, proton magnetic resonance (H-1 NMR), FT-IR spectroscopy and optical observations. They undergo two temperature induced solid-solid structural phase transitions. The first one, quasi-continuous (with temperature hysteresis below 1 K), occurs at 324 K in ImIA and 327 K in ImIB, and the second one, clearly of the first order, at 273/278 (cooling/heating) and 291/295 K, in ImIA and ImIB, respectively. Ferroelastic properties are maintained in low-temperature phases. Both materials are isomorphic in the corresponding phases. High temperature phase I has a hexagonal P63/mmc symmetry, and phase II has orthorhombic Cmcm. The crystal architecture is composed of discrete, face-sharing bioctahedra [M2I9](3-) (M: Sb, Bi) and imidazolium cations which are highly disordered over phases I and II. The dynamics of the imidazolium cations has a prominent impact on the stability of the particular phases.
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